Method of making phenolic thioethers



United States Patent 3,303,209 METHOD OF MAKING PHENOLIC THIOETHERS Walter Reifschneider, Midland, and Jacqueline S. Kelyman, Auburn, Mich., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Filed Feb. 18, 1966, Ser. No. 528,408

' 5 Claims. (Cl. 260-465) wherein Ar is a 6- or 10-carbon aromatic hydrocarbon nucleus, R is loweralkyl, loweralkenyl, loweralkynyl, cycloalkyl of from 3 to 6, both inclusive, carbon atoms, ar-loweralkyl, phenyl, loweralkoxy, phenoxy, hydroxy, halo, nitro, cyano, amido, loweralkoxycarbonyl, or loweralkanoyloxy, benzoyloxy, or phenoxycarbonyl, and

Wherein R is loweralkyl, loweralkenyl, loweralkynyl,

cycloalkyl of from 3 to 6, both inclusive, carbon atoms, haloloweralkyl, ar-loweralkyl or lower alkanoyl, and n is an integer of from Oto 4, both inclusive. The nucleus Ar is such that the present compounds are all substituted benzene or naphthalene derivatives.

The products of the present invention have numerous uses. Those in which unsaturated components appear are useful as monomers or co-monomers in the synthesis of polymeric, including copolymeric substances. The compounds themselves are insecticidal, although some are substantially more active in this use than are others. Various of the compounds possess herbicidal properties. The compounds are germicidal. 'They are useful in reactions with phosphonyl chloride or thiophosphonyl chloride or any of a number of their derivatives, in the production of phosphate or thiophosphate compounds.

The fundamental aspect of the present discovery is that an arenol, broadly, and more particularly a (thiocyanato) phenol or substituted (thiocyanato)phenol or a corre-- sponding naphthol derivative reacts, in the presence of a base, at the (thiocyanato) site with a haloaliphatic compound in some way to obtain, at the site formerly occupied by' the (thiocyanato) group a thioether substituent upon the phenol or naphthol while leaving the phenolic hydroxyl site essentially unreacted. Halogenated aliphatic compounds'of a wide range are useful; the halohydrocarbons are representative but not definitive. The general reaction of the present invention is thus represented by the following equation:

wherein X is a halogen and n, R and R have the meanings hereinbefore set forth. A naphthol can be used instead of a phenol. The reaction appears to involve a metathesis of some sort but byproducts of reaction have not yielded easily to attempts to identify them.

Because the present reaction involves only the (thiocyanato) group of the arenol, virtually any naphtholic or phenolic compound possessing this group can be used. In addition to the position isomers of the hydroxyaryl thiocyanates, the various alkylhydroxyaryl thiocyanates can be employed. Also, with equally good results, the various base 3,303,209 Patented Feb. 7, 1967 alkenyl and alkynyl hydroxyaryl thiocyanates are employed. Also, such ethers as the alkoxyor aryloxyhydroxyaryl thiocyanate compounds are employed as starting materials with good results. It is to be understood that the alkoxyor aryloxy-portion is in addition to, not at the expense of, the aromatic hydroxy group. Also aryl substituents upon the hydroxyaryl thiocyanate nucleus are acceptable. Similarly, such other substituents as may affect the properties of the resulting products but do not interfere with the reaction at the thiocyanato-site can be present upon the hydroxyphenyl ring; these include the cyano radical, amido structures, and the ester structure presently identified as loweralkoxycarbonyl, and phenoxy carbonyl. These latter designations indicate monovalent organic radicals of the formula also the reverse esters, with the lower alkanoyloxy and benzyloxy substituents.

Commonly the thiocyanato radical is in a position para with respect to the aromatic hydroxyl group; but this is immaterial in the present invention.

As base, there can be employed the bases commonly known and used; alkali metal hydroxides, alkali metal alkoxides, alkali metal carbonates, basic ion exchange agents, strong amines, and so forth. The identity of the base does not appear to be critical; in general it is advantageous that the base be strong.

As to the haloorganic compound, it is critical that the halogen be relatively available for reaction. This requirement is consistently met when the halogen is bonded to an aliphatic group or moiety but usually fails to be met when the halogen is bonded to an aromatic nucleus. Thus a halobenzene will not enter the present reaction as halo organic compound, whereas a haloalkane does so readily. Halogen on analiphatic side chain on an aromatic nucleus reacts readily. Thus in an oc,4dlCl1lOIOtOl116IlC, the aliphatic a-chlorine reacts readily in the present synthesis, whereas the aromatic 4-chlorine does not, even under exalted conditions.

The nature of the site to which the halogen is bonded is much more important than the identity of the halogen. Fluorine, despite the stability of its bond with organic moieties, is satisfactory. Chlorine, by reason of its low cost and excellent performance, is often preferred. Bromine reacts very readily but is more expensive than chlorine and sometimes sterically hindered in situations that admit of the use of chlorine. Cost and steric hindrance also aifect'a decision to employ iodine, but it is available as a reactive halogen.

The reactivity of the halogens varies approximately directly as molecular weight. Thus in a chlorobromo aliphatic compound, the bromo site reacts first and, absent other obvious factors such as steric hindrance, in the presence of less than an excess of (thiocyanato) phenol or naphthol compound, almost exclusively. In the presence of a stoichiometric excess of the (thiocyanato) phenol or naphthol, the bromo site reacts first, and the chloro site thereafter. Similarly, fluorine is, in general, least reactive, and iodine most. Thus the position of substituents and the course of alternative reactions can to a large extent be controlled.

The reactants can be combined in any order or sequence. Advantageously, the base that drives the reaction forward is added last. Mixtures of reactants containing less than all the reactants can be prepared in advance and held for later use, to be mixed into a complete reaction mixture as desired, although mixtures of the (thiocyanato) phenol and base should be used in not morethan a few hours, if excessive amounts of byproducts are to be avoided. Reaction begins and product begins to be prepared as the reaction mixture is completed.

Because the present reaction is believed to have been unknown hitherto, some doubt existed at first, as to the identity of products. Careful studies characterizing products have been made.

Products have been characterized by such traditional methods as mixed-melting-point determinations with au thentic samples of compounds of assigned structure, infrared spectroscopy, preparation of derivatives, and other physical and chemical methods.

The reaction follows the indicated course, goes forward smoothly, obtains good yields, and makes efiicient use of starting materials. Upon combining the reactants, the reaction goes forward at a good rate at temperatures as low as C. It proceeds at a good rate at room temperature, and usually reaches completion in from two to four hours, depending upon the identities and quantities of reactants employed, actual temperature, whether stirring is employed and other known factors. At lower temperatures, times of up to 200 hours may be desired for good yield, whereas at superambient reflux temperatures in solvent, shorter times may give good results. Higher temperatures seem to cause the reaction to go forward more rapidly over ordinary ranges of organic chemical reaction temperatures.

Some of the desired product is formed immediately upon the contacting together of the reactants and when small yield of product in the presence of relatively large amounts of unconsumed starting material is satisfactory, the reaction mixture can be employed in crude form shortly after the combining of the reactants to obtain at least minimum benefits according to the present invention. If desired, the reaction may be permitted to go forward to a desired degree of completion or to its natural termination point, typically to the exhaustion of any limiting reactant, and the crude reaction mixture thereof subsequently employed.

When it is desired to obtain products in highly purified form, the reaction mixture can be warmed, optionally under subatmospheric pressure, to vaporize and remove liquid reaction medium, if any, and the resulting productcontaining residue stirred into a mixture of ice and concentrated non-oxidizing mineral acid. Typically, ice melts or partially melts, diluting the acid, which acid also neutralizes any unconsumed base. The use of ice limits the rise of temperature to a temperature which is not injurious to desired product. However, the product is not usually highly heat-sensitive.

From such ice and acid treatment, product typically separates as in immiscible solid, as a gum or oil, or as a liquid.

When product separates in the acid-ice mixture as a solid, it is conveniently collected by permitting the ice to melt completely, filtering the resulting mixture, to recover the typically insoluble solid product, which can then be used as a partially pure substance. When greater purity is desired, the purification can employ also washing with water and drying and thereafter recrystallizing the residue from the filtration in a suitable solvent such as methyl cyclohexane, benzene or a petroleum fraction boiling in the temperature range of 60-70 C. or a mixture of these, and so forth.

When the product separates from the ice and acid mixture as a gum or oil, the aqueous mixture can be conveniently extracted with solvent. This can be any of a large-number of organic solvents, a re-crystallization solvent, or diethyl ether. The solvent or ether layer is then separated. The separated layer is thereafter washed with water to remove traces of acid, and can also be washed with saturated sodium chloride solution. The resulting washed solution can then be dried over anhydrous sodium sulfate and thereafter warmed to vaporize and remove solvent by evaporation and the resulting residue recrystallized from a suitable solvent, or, if more convenient, distilled under subatmospheric pressure.

When the product separating in the acid-ice mixture is a liquid, the same procedures as are employed in the purification of a gum or oil are employed with good results.

When there is no requirement that product be distinctly pure, starting materials of mixed identity can be employed. Thus when, as in some industrial productions, it is satisfactory to prepare a thioether of mixed identity and only generally conforming to an average analysis, starting materials of only generally known identity can be employed and the resulting mixed product utilized with or without purification.

Over the methods known in the prior art, the present method offers numerous advantages. It permits conversion from a phenol or naphthol or substituted phenol or substituted naphthol into the corresponding thioether phenol or thioether (substituted) phenol or corresponding naphthol derivative in but two steps: thiocyanation and the present process.

The new method, by its brevity and simplicity, permits preparation of thioether phenols and thioether naphthols and their substituted derivatives in a range of variety hitherto unavailable.

Skilled analytical chemists will thus recognize that the process of the present invention lends itself to be employed in the preparation of special derivatives of aliphatic halogen-containing compounds or compounds believed to contain halogen whereby the hydroxy phenylthio or hydroxynaphthylthio group is introduced into such compounds at the halogenated site, With the result that the derivatives are frequently not only of substantially higher melting or boiling point, but also well-adapted to, for example, spectrum analysis of various kinds.

So long as the reacting substances employed in the present process meet the definitions foregoing and are not obviously of such nature as to be repugnant to skilled chemists, the method of this invention is operable. However, the greater the total molecular weight and the larger the molecule, the less definitive of it the thiocyanato and halo starting groups are, and the less the thioether linkage is believed to influence the properties of the resulting product. Therefore, the more definitive starting and product substances are those of molecular weights commonly encountered in organic chemistry, such as molecular weights of a few hundred.

Thus the preferred and most typical starting materials and products, when they carry substituents having carbon chains, will be those of which the carbon chains are of a lower order, that is, up to and including six carbon atoms each. Somewhat more latitude is admissable in the haloaliphatic backbone of the haloaliphatic compound Here, R, including substituents as hereinbefore defined, can be of a total of up to twelve carbon atoms.

The following preparations illustrate the best aspects of the present invention now known to the inventors, but are not to be considered as limiting thereof.

Example! 1.Pre'parafi0n of p-(methylthio) phenol A first solution was prepared by adding 13.8 grams (0.6 mole) metallic sodium to 175 milliliters methanol to obtain a solution of 0.6 mole of sodium methoxide in substantial excess methanol as base and solvent. A second solution was prepared consisting essentially of 30 grams (0.2 mole) p-(thiocyanato)phenol and 28.4 grams (0.2 mole) methyl iodide dissolved in milliliters methanol. The said first solution was added as a small, slow stream with continuous stirring to the second said solution to obtain a reaction mixture. Upon the completion of the preparation of the reaction mixture, the resulting mixture Was heated at its boiling temperature and under reflux for approximately 2 hours to drive the reaction to completion. Upon the completion of the reaction, excess methanol as solvent was vaporized and removed, and the resulting residue poured into a mixture of ice and concentrated hydrochloric acid. Basic sub stances were neutralized and water-soluble neutralization products obtained, and the desired p-(methylthio)phenol product separated as an insoluble solid which was collected from the aqueous liquid by filtration. The solid residue was taken up from the filter in, and recrystallized from, a mixed solvent system of which the solvent components 'Were benzene and a mixed aliphatic hydrocarbon fraction boiling in a 6070 C. temperature range. As a result of these procedures there was obtained 14.5 grams (51 percent by weight of starting p-(thiocyanato)phenol of a p-(methylthio)phenol product melting at 8485 C. The melting point for this substance in the published literature is 8485 C. although the literature process for its preparation required 6 steps and 8 original reactant substances.

All the products of the present invention can be prepared in essentially the same manner.

In procedures essentially the same as the foregoing, employing 4-thiocyanato-1-naphthol with methyl iodide there is obtained a 4-methylthio-l-naphthol as off-White crystals melting at 105107 C.

Example 2.Preparati0n: of p- (cyclopropylthio)phenol A solution is prepared consisting essentially of 30 grams (0.2 mole) p-(thiocyanato)phenol and 15.3 grams (0.2 mole) chlorocyclopropane (boiling at 41 C.) in 150 milliliters methanol. A second solution is prepared consisting essentially of 50 grams (0.75 mole) potassium hydroxide of approximately 85 percent purity, in 150 milliliters of water.

The aqueous potassium hydroxide is added in a slow stream to the said first solution to obtain a reaction mixture. When the addition is complete, the resulting reaction mixture is stirred continuously at room temperature for 10 hours. At the end of the 10 hour reaction time, the resulting mixture is gently warmed under sub-atmospheric pressure to vaporize and remove methanol and the resulting aqueous residue is poured into a mixture of ice and concentrated hydrochloric acid in an amount in excess of that equivalent to the employed potassium hydroxide. As a result of these operations, the ice melts and, from the resulting aqueous solution, upon standing, there separates a solid product which is collected by filtration, taken up from the filter paper in methanol and recrystallized from a methanol-water mixture to obtain a p-(cycl0propylthio)phenol as a white crystalline solid product. The yield is approximately 50 percent by weight of starting p-(thiocyanato)phenol. The product is germicidal.

In proceduressimilar to the foregoing, employing 1- chloro-n-hexane (boiling at 132 C.) there is obtained a white, crystalline solid, a p-(n-hexylthio)phenol product.

Example 3.2,6-dichl0ro-4-(methylthio) phenol A first solution is prepared consisting essentially of 50 grams (0.75 mole) 85 percent pure potassium hydroxide dissolved in 150 milliliters water. A second solution is prepared consisting essentially of 55 grams (0.25 mole) 2,6-dichlor-o-4-(thiocyanato)phenol, and 35.5 grams (0.25 mole) methyl iodide dissolved in 300 milliliters methanol.

The said first solution is added as a small, slow stream continuously and with stirring over a period of time to the said second solution to obtain a reaction mixture. Upon the completion of the preparation of the said reaction mixture, the resulting solution is stirred continuously at room temperature for approximately 2 hours to carry the reaction to completion and obtain the desired product. At the conclusion of 2 hours reaction time, methanol is vaporized and removed and the resulting residue is taken up in a mixture of ice and excess concentrated hydrochloric acid. From the resulting aqueous solution a solid pro-duct material separates and is collected by filtration, taken up in methanol and recrystallized from a methanol-water system to obtain 49 grams of a 2,6-dichloro-4-(methylthio)phenol product. The yield represents 94 percent conversion of the starting 2,6-dichloro-4-(thiocyanato)phenol. The product melts at 54-56" C. Upon analysis, a product representative of this example was found to have a content of carbon and hydrogen of 40.38 and 2.78 percent, respectively, as compared with theoretical values of 40.21 and 2.89 percent, respectively. The assigned structure was confirmed by infrared spectrum analysis.

Example 4 In procedures essentially the same as those of Example 2, but employing 23.7 grams (0.2 mole) chlorocyclohexane (boiling at 142 C. under 760 millimeters pressure) there is obtained, as a white crystalline product p-(cyclohexylthio)phenol. The substance melts at 63.5 C.

Example 5 .-2-br0m0-6-ch l0r0-4- (methylthio) phenol A first solution is prepared consisting essentially of 34.2 grams (0.34 mole) triethylamine dissolved in 75 milliliters methanol. This is employed as the base needed in the present reaction. A second solution is prepared consisting essentially of 30 grams (0.113 mole) 2-brorno- 6-chl0ro-4-(thiocyanato)phenol and 16.1 grams (0.113 mole) methyl iodide disolved in 125 milliliters methanol. The first said solution is added as a small, sloW stream continuously and With stirring to the said second solution to obtain a reaction mixture. Upon the completion of the preparation of the said reaction mixture, the resulting solution is stirred continuously as it is heated at its reflux temperature, about 6070 C., for approximately 2 hours to carry the reaction to completion and obtain the desired product. At the conclusion of 2 hours reaction time, methanol solvent is vaporized and removed and the resulting residue is poured into a mixture of ice and excess concentrated hydrochloric acid. The resulting aqueous solution is extracted with three 200 milliliter portions of diethyl ether, the ether extracts combined, Washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. Ether is vaporized and removed and the resulting product distilled under subatmospheric pressure. As a result of these operations there is obtained a 2-bromo-6-chloro-4- (methylthio) phenol product as a white crystalline solid. The compound melts at 4344.5 C. The assigned structure Was confirmed by infrared spectrum analysis.

Example 6.p-(Allylthio) phenol A first solution is prepared consisting essentially of 146.2 grams (1 mole) p-hydroxyphenyl thiocyanate and 76.5 grams (1 mole) allyl chloride dissolved in ethanol (500 milliliters). A second solution is prepared consisting essentially of 40 grams (1 mole) sodium hydroxide dissolved in milliliters water. The second said solution is added as a small, slow stream continuouly and with stirring over a period of time to the said first solution to obtain a reaction mixture. Upon the completion of the preparation of the said reaction mixture, the resulting solution is stirred continuously at ambient temperature (2124 C.) for approximately 1 hour reaction time to carry the reaction to completion and obtainthe desired product. Upon the conclusion of the reaction time, the resulting mixture is warmed in a vacuum evaporator and solvents are vaporized and in large part removed, and the resulting residue is poured into a mixture of ice and excess concentrated hydrochloric acid. From the resulting aqueous solution, an oily product material separates and is collected by ether extraction. Ether extract is warmed to vaporize and remove ether; the resulting oily product is taken up in and recrystallized from hot ethanol as it cools, to obtain a p-(allylthio)phe- 1101 product as white crystals. The compound melts at 4243 C.

In procedures essentially the same as those foregoing, but employing 2-chloropentene, there is obtained a p-((1- methylenebutyl thio phenol product.

Example 7.4-(2-propynylthi0)-3,5-xylenol A first solution is prepared consisting essentially of 10.2 grams (0.1 mole) triethylamine disolved in 25 milliliters ethanol. A second solution is prepared consisting essentially of 17.5 grams (0.1 mole) 4-thiocyanato-3,5 xylenol, and 11.9 grams (0.1 mole) 3-bromopropyne-2 dissolved in 200 milliliters ethanol. The first said solution is added as a small, slow stream continuously and with stirring over a period of time to the said second solution to obtain a reaction mixture. Upon the completion of the preparation of the said reaction mixture, the resulting solution is stirred continuously at room temperature for approximately 3 hours reaction time to carry the reaction to completion and obtain the desired product. At the conclusion of the reaction time, ethanol is vaporized and removed and the resulting residue is poured into a mixture of ice and excess concentrated hydrochloric acid. From the resulting aqueous solution, a solid product material separates and is collected by filtration, taken up in hot ethanol and recrystallized therefrom with cooling to obtain a white, crystalline 4-(2-propynylthio)3,5-xylenol product. The product is a crystalline solid melting at 64.565:5 C. The assigned structure is confirmed by infrared spectrum analysis.

The hydroxyphenyl thiocyanate (which may also be called a (thiocyanato)phenol) reactant of choice can readily be selected by selecting such compound wherein the (thiocyanate) group occupies the position whereinto it is desired to introduce the moiety characteristic of the products of the present invention.

T-he halo-organic compound reactant of choice can readily be selected by choosing the compound whereof R has the identity of the thioetherifying moiety it is desired to introduce into the product compound and X is halogen chosen-for convenience.

In view of the detailed statements of the best methods now known, as hereinbefore set forth, and with the guidance of the foregoing comments on selection of reactants, skilled chemists can readily prepare desired other products according to the present process.

The following are representative of starting materials thus elected, and their products.

Employing 3-fluoro-4-(thiocyanato)phenol and by sparging methyl bromide gas thereinto, in methanol solution in the presence of sodium methoxide, a white, crystalline 3-fluoro-4-(methylthio)phenol product.

Repeating the above but using 3-chloro-4-(thiocyanato)- phenol, a 3-chloro-4-(methylthio)phenol product as a white crystalline solid melting at 66.5-68 C.

Employing 2-(methylthio)-4-thiocyanatophenol, and with methyl iodide, there is obtained a 2,4-bis-(methylthio) phenol product as an oily liquid. Upon crystallization from solvent the product is a white, crystalline solid melting at 40-41 C.

From bromoethane and 2-cyano-4-hydroxyphenyl thiocyanate, a 3-cyano-4-(ethylthio)phenol product.

From l-bromo-Z-ehloroethane and 2-tphenyl-4-(thionoyl chloride, a 3-cyclopentyl-4-hydroxyphenylthiooctanoate.

From S-hydroxy-Z-thiocyanatobenzamide and chlorocyclohexane, S-hydroxy-Z-cyclohexylthiobenzamide.

From 3-ethynyl-4-thiocyanatophenol and iodomethane,

3-ethynyl-4- methylthio phenol.

From 2-hexyl-5-thiocyanatophenol and 3-bromo-propyne, 2-hexyl-5-(Z-propynlthio) phenol.

From 2-butoxy-4-thiocyanatophenol and 1-bromo-3,3- dichloro 2 methylpropane, 2 butoxy 4 (3,3 dichloro-2-methylpropylthio)phenol.

From 2-phenoxy-5-thiocyanatophenol and ethyl iodide, 5-ethylthio-2-phenoxyphenol.

From 2-hydroxy--thiocyanatophenol and l-fluoro-nhexane (boiling at 92-93 C. under standard conditions), 2-hexylthio-6-hydroxyphenol.

From 5-iodo-2-thiocyanatophenol and an approximately mono-chlorinated mixture of mixed aliphatic petroleum hydrocarbons of approximately 6 to 10 carbon atoms per molecule, a Z-(mixed C -C alkyl)thio-S-iodophenol.

From methyl-2-hydroxy-5-thiocyanato-benzoate and bromododecane, methyl (5-dodecylthio-2-hydroxy)benzoate.

From hexyl (2-hydroxy-4-thiocyanato)benzoate and methyl iodide, hexyl (2-hydroxy-4-methylthio)benzoate.

From (Z-hydroxy-S-thiocyanatophenyl)benzoate and methyl iodide, (2-hydroxy-5-methylthiophenyl)benzoate.

From 2-hexylthio-4-thiocyanatophenol and methyl iodide, 2-hexylthio-4-methylthio)phenol.

The substituent R can, thus, also be loweralkylthio.

Also, in manners similar to the foregoing and employing a dihalohydrocarbon of the formula X R, and a total of two molecular proportions of (thiocyanato)phenol, bis compounds of the type Rn Rn are prepared. When the hydroxyphenolthio moieties are to be alike, the dihalo compound XR' can have both halogens alike or different, one molecular proportion is employed, and the (thiocyanato)phenol is employed in two molecular proportions. For example, employing 2 moles of p-hydroxy-phenylthiocyanate and one mole of 1,2-dibromoethane there is obtained a 1,2-bis(p-hydroxyphenylthio)ethane.

When the hydroxyphenylthio moieties are to be unlike the halogens of the compound XR are also unlike, the heavier halogen reacting first. Such reaction, employing equimolecular amounts of reactants, obtains a hydroxyphenylthiohaloorganic compound of which the foregoing 4-(2-chloroethyl) thio-Z-phenylphenol is representative, the active halogen-here the chloro on the chloroethyl moietyc an then further be caused to react with further (thiocyanato) phenol the same or different, to obtain a his compound, of which the hydroxy phenylthio groups are unlike. For example, by causing the foregoing 4-(2-chloroethyl)thio-2-phenylphenol to react with 3-chloro-4-hydroxyphenyl thiocyanate, one obtains a 4- (3 chloro 4 hydroxy(phenylthio)ethyl)thio 2- phenylphenol product. This is a white, crystalline solid of distinct odor and is a highly efiective germicide.

We claim: 1. Method of preparing phenolic thioethers of the general formula:

SR which comprises contacting a compound of the formula:

cycloalkyl of from 3 to 6, both inclusive, carbon atoms, ar-loweralkyl, phenyl, loweralkoxy, phenoxy, hydroxy,

halo, nitro, cyano, amido, loweralkoxyc-arbonyr, or loweralkanoyloxy, benzoyloxy, or phenoxycarbonyl,

and wherein R is loweralkyl, loweralkenyl, loweralkynyl, cycloakyl of from 3 to 6, both inclusive, carbon atoms, haloloweralkyl, ar-loweralkyl or loweralkanoyl, n is an integer of from 0 to 4, both inclusive, and m is an integer 1 or 2.

2. Method of claim 1 wherein the contacting is carried out in a liquid reaction medium.

3. Method of claim 2 wherein the compounds in contact are heated together for at least a part of the period of time at a superambient temperature.

4. Method of claim 1 wherein m is the integer 2.

5. Method of claim 4 wherein the compound being of the identity in the second portion different from that in the first.

No references cited.

CHARLES B. PARKER, Primary Examiner.

D. R. PHILLIPS, Assistant Examiner. 

1. METHOD OF PREPARING PHENOLIC THIOETHERS OF THE GENERAL FORMULA: 